White pigments were abundantly used in 20th century paintings, and relate to several degradation risks such as titanium white mediated photocatalytic binder degradation or zinc soap formation. Knowledge about the white pigments that were used is essential for risk assessments of 20th century collections. In this study, a representative set of 179 paintings in Dutch modern art collections were analyzed by portable X-ray fluorescence spectrometry. Subsequent explorative data analysis was performed, supported by qualitative findings from 140 home-made reference samples. Micro-samples were further investigated by X-ray diffraction and scanning transmission electron microscopy to gain information about crystal structure and surface coating. This study reveals that Dutch 20th century artists were hesitant to use titanium white. In the Netherlands, the use of this pigment is observed convincingly from the 1970s onward and initially mostly in non-oil binders. Additionally, lead white was used until late in the 20th century for paints and grounds but rarely mixed with titanium white in paints. The study also indicated that many CoBrA artists used zinc white, underlining the risk of degradation due to soap formation. Furthermore, this study highlights the different production processes of titanium white. Through the association of titanium with niobium, an impurity only present for sulfate processed pigments, the production process can be identified. The absence of niobium indicates the presence of rutile and is thus a sign of paint stability, as well as a ‘post 1959’ dating. This explorative study illustrates the value of a combination of data analysis approaches, which includes assessment of spectra as well as descriptive, bivariate and multivariate analysis, for medium-sized datasets gathered at similar conditions.@en

This study reports on the effect of artists’ paint formulation on degradation rates of TiO2-based oil paints. Titanium white oil paint exists in a multitude of different recipes, and the effect of the formulation on photocatalytic binder
degradation kinetics is unknown. These formulations contain, among others, one or both titanium dioxide polymorphs, zinc oxide, the extenders barium sulfate or calcium carbonate and various additives. Most research performed
on the photocatalytic degradation process focusses on pure titanium white-binder mixtures and thus does not take into account the complete paint system. Since photocatalytic oil degradation is a process initiated by the absorption of UV light, any ingredient or combination of ingredients influencing the light scattering and absorption properties of the paint films may affect the degradation rate. In this study three sets of experiments are conducted,
designed using the design of experiments (DoE) approach, to screen for the most important formulation factors influencing the degradation rate. The benefits of using DoE, compared to a more traditional ‘one factor at a time approach’ are robustness, sample efficiency, the ability of evaluate mixtures of multiple components as well as the ability to evaluate factor interactions. The three sets of experiments investigate (1) the influence of the TiO2 type, (2) the impact of different mixtures of two types of TiO2, ZnO and the additive aluminum stearate and (3) the influence of common extenders in combination with photocatalytic TiO2, on the photocatalytic degradation of the oil binder. The impact of the formulation on the degradation rate became apparent, indicating the shortcoming of oversimplified studies. The protective effect of photostable TiO2 pigments, even in a mixture with photocatalytic TiO2 pigments, as well as the negative effect of extenders was demonstrated. Furthermore, the ambiguous role of ZnO (photocatalytic or not) and aluminum stearate is highlighted. Neither can be ignored in a study of degradation behavior of modern oil paints and require further investigation.@en

Twentieth century paints often contain titanium dioxide and zinc oxide based white pigments that can range from photostable to highly photocatalytic. Photocatalytic pigments can cause the degradation of paint upon UV exposure, whereas photostable pigments may be benign or can protect paintings from degradation. Hence, knowing whether or not a pigment is photocatalytic is of high importance for risk assessment and the subsequent decision making process concerning storage and exposure conditions of objects. Here we present a proof of principle, focused on titanium white paints, for an easy-to-use and low-tech application of a commercial photocatalytic activity indicator ink (PAII) on embedded paint samples or cross sections. This test determines, qualitatively, if a photocatalytic pigment is present in a white paint sample. The PAII paint sample staining application shows an obvious color change, within five minutes of UV irradiation, for paint samples containing photocatalytic pigments. A microscope with a camera and a UV source are the only necessary equipment for the application of this method. A quantitative image processing protocol is also proposed as an extension of the staining method by applying open source software analysis to measure the color change using photographs. The test was evaluated on reference paints with well-characterized pigments and applied on samples from modern paintings by Piet Mondriaan, Robert Ryman, and Lucebert, indicating the presence of harmful photocatalytic pigments in these cases. The novel application of a commercial ink on paint samples offers a simple test, not just for assessment of photocatalytic activity of titanium white pigments, but which may in future be applied for the detection of photoactive forms of zinc white and other potentially harmful semiconductor pigments in art objects.

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Titanium white (TiO₂) has been widely used as a pigment in the 20th century. However, its most photocatalytic form (anatase) can cause severe degradation of the oil paint in which it is contained. UV light initiates TiO₂-photocatalyzed processes in the paint film, degrading the oil binder into volatile components resulting in chalking of the paint. This will eventually lead to severe changes in the appearance of a painting. To date, limited examples of degraded works of art containing titanium white are known due to the relatively short existence of the paintings in question and the slow progress of the degradation process. However, UV light will inevitably cause degradation of paint in works of art containing photocatalytic titanium white.In this work, a method to detect early warning signs of photocatalytic degradation of unvarnished oil paint is proposed, using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Consequently, a four-stage degradation model was developed through in-depth study of TiO₂-containing paint films in various stages of degradation. The XPS surface analysis proved very valuable for detecting early warning signs of paint degradation, whereas the AFM results provide additional confirmation and are in good agreement with bulk gloss reduction.

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